CN111377786B - Method for oligomerization of isobutene - Google Patents

Method for oligomerization of isobutene Download PDF

Info

Publication number
CN111377786B
CN111377786B CN201811622912.7A CN201811622912A CN111377786B CN 111377786 B CN111377786 B CN 111377786B CN 201811622912 A CN201811622912 A CN 201811622912A CN 111377786 B CN111377786 B CN 111377786B
Authority
CN
China
Prior art keywords
acid
titanium
composite oxide
catalyst
based composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811622912.7A
Other languages
Chinese (zh)
Other versions
CN111377786A (en
Inventor
霍稳周
吕清林
姜睿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
Original Assignee
China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Dalian Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN201811622912.7A priority Critical patent/CN111377786B/en
Publication of CN111377786A publication Critical patent/CN111377786A/en
Application granted granted Critical
Publication of CN111377786B publication Critical patent/CN111377786B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The method for oligomerization of isobutene uses heteropoly acid/titanium-based composite oxide as catalyst, in which the titanium-based composite oxide is selected from TiO 2 ‑Al 2 O 3 、TiO 2 ‑SiO 2 And TiO 2 ‑ZrO 2 At least one heteropolyacid selected from the group consisting of at least one of phosphotungstic acid, silicotungstic acid, arsotungstic acid, germanotungstic acid, phosphomolybdic acid, silicomolybdic acid, arsenomolybdic acid and germanomolybdic acid. The method can realize continuous production, has simple and convenient operation in the reaction process, has the advantages of high conversion rate, good dimer selectivity and the like when being used for the isobutene oligomerization reaction, and is a new green and environment-friendly process.

Description

Method for oligomerization of isobutene
Technical Field
The invention relates to an isobutene oligomerization method, in particular to a method for catalyzing isobutene oligomerization reaction by using heteropoly acid/titanium-based composite oxide as a catalyst.
Background
At present, isobutene is mostly used for synthesizing methyl tert-butyl ether (MTBE) and is used as a blending component of high-octane motor gasoline. However, this method using isobutylene has become unreasonable due to the serious pollution effect of methyl t-butyl ether on groundwater. Thus, is C 4 The isobutene in the fraction has very important practical significance for seeking a more reasonable utilization way.
The oligomerization of low-carbon olefin is one of the important chemical processes in the oil refining and organic chemical industry, wherein the oligomerization product of butylene is an important chemical intermediate, can be used for producing oligomerization gasoline and diesel oil, and can also be used as an important intermediate for producing detergents, plasticizers, additives and pesticides.
Isobutene oligomerization is a typical acid-catalyzed reaction, and the catalysts mainly comprise a liquid acid catalyst and a solid acid catalyst. When liquid acid catalysts (sulfuric acid, methyl benzenesulfonic acid and the like) are adopted in the early stage, the reaction selectivity is poor, the purity of the product isobutene dimer is low, the catalysts are not easy to separate, the equipment is corroded, and the production process continuity is difficult to realize. In recent years, solid acid catalysts have become the hot spot of research on oligomerization of isobutene, and mainly include solid phosphoric acid catalysts, oxides and composite oxide catalysts, molecular sieve catalysts, ion exchange resin catalysts, supported sulfate catalysts, solid super acidic catalysts and the like.
The traditional solid phosphoric acid catalyst is generally prepared by taking diatomite as a carrier and loading strong phosphoric acid (or called polyphosphoric acid), has been applied to petrochemical aspects such as olefin oligomerization for decades, and has exposed a plurality of problems in the long-term application process, such as poor water resistance, low mechanical strength, easy argillization and the like.
Many metal oxides and composite oxides can catalyze oligomerization of isobutene, and binary composite oxide A1 with strong acidity 2 O 3 -SiO 2 ，TiO 2 -SiO 2 ，ZrO 2 -SiO: has both B acid center and L acid center, wherein A1 with high acidity 2 O 3 -SiO: has good catalytic activity in the oligomerization reaction of isobutene.
The molecular sieve is aluminosilicate with high crystallinity, has regular pore structure, uniform surface acid center distribution, moderate acidity and good activity in oligomerization of isobutene. The types, the silicon-aluminum ratio, the contained metal ions, the pore structure, the reaction conditions and the like of the molecular sieve have influence on the activity and the selectivity of the isobutene oligomerization reaction.
The supported sulfate is a solid acid with wider application, and a plurality of metal sulfates can generate a considerable amount of acid centers with medium strength after being calcined, so that the conversion rate of isobutene is high and the selectivity of dimers is lowest when the supported sulfate is used for isobutene oligomerization.
The solid super acidic catalyst catalyzes the oligomerization reaction of isobutene, the reaction is carried out in liquid phase, isobutene can be completely converted at low space velocity, and products mainly comprise di-trimer and trimer, but still contain tetramer with a certain proportion.
The ion exchange resin is a novel solid acid catalyst, and has the advantages of stable catalytic effect, no corrosion, no pollution, low price and the like, so that the ion exchange resin is widely applied to reactions such as etherification, esterification, superposition, hydration, alkylation and the like.
US4100220, US4463211 report cation exchange resin catalyst as catalyst for butene oligomerization, but high molecular weight oligomer blocks reaction channel easily, and alkylation of resin skeleton causes rapid activity decrease, and furthermore, the resin has poor high temperature resistance, which limits its application. The CA2435590A1 patent describes a process for obtaining high purity diisobutylene by reducing the acid capacity of the catalyst using NaOH, using a macroporous sulfonic acid resin as the catalyst and pure isobutylene as the starting material. Chinese patent CN107754852A provides a method for modifying a strong acid cation exchange resin catalyst by a silicophosphate solution.
2017, volume 3 of volume 33 reports that sodium exchange Amberlyst-15 catalyzes isobutene to prepare diisobutylene by means of superposition, and the results show that the conversion rate of isobutene is gradually reduced along with the increase of the sodium exchange rate, the selectivity of a dimerization product is rapidly increased, and the conversion rate of isobutene and the number of acid centers on a catalyst are in a linear relationship. The reaction temperature is increased, the conversion rate of isobutene on resin catalysts with different sodium exchange rates is increased, the dimerization selectivity is reduced, and the higher sodium exchange rate enables the selectivity of dimerization products on the resin to be reduced along with the change range of the temperature. The space velocity is increased, the selectivity of dimerization products is increased, and the conversion rate of isobutene is reduced.
Petrochemical 2007, volume 36, phase 3 reports that strong-acid cation exchange resin in tertiary butanol catalyzes oligomerization kinetics of isobutylene, and oligomerization kinetics of isobutylene (m) in a system of strong-acid cation exchange resin (catalyst) and tertiary butanol is studied. The results show that isobutylene oligomerization has the feature of first order series irreversible. The tertiary butanol is added into the reaction system, although the acidity of the catalyst can be reduced, the adsorption capacity of isobutene on the surface of the catalyst is improved, so that the selectivity of a dimer (trimethylpentene) of isobutene is obviously improved, and the conversion rate is reduced to some extent.
Disclosure of Invention
Aiming at the problem of low dimer selectivity in the isobutene oligomerization reaction in the prior art, the invention provides the isobutene oligomerization method, which adopts heteropoly acid/titanium-based composite oxide as a catalyst, has good reaction performance and high dimer selectivity.
The technical purpose of the invention is realized by the following technical means:
the oligomerization method of isobutene uses heteropolyacid/titanium-base composite oxide as catalyst, in which the titanium-base composite oxide is selected from TiO 2 -Al 2 O 3 、TiO 2 -SiO 2 And TiO 2 -ZrO 2 At least one heteropolyacid selected from at least one of phosphotungstic acid, silicotungstic acid, arsenotungstic acid, germanotungstic acid, phosphomolybdic acid, silicomolybdic acid, arsenomolybdic acid and germanomolybdic acid.
In the above method, the weight ratio of the heteropolyacid to the titanium-based composite oxide in the catalyst is from 0.05 to 1:1, preferably from 0.1 to 1 to 0.9, and most preferably from 0.3.
In the above process, tiO in the titanium-based composite oxide 2 The content of (b) is 10% to 90%, preferably 15% to 85%, most preferably 30% to 75% by weight.
In the above method, the heteropoly acid/titanium-based composite oxide catalyst is prepared by the following method:
(1) Preparing a titanium-based composite oxide by adopting a coprecipitation method: preparing solution by taking corresponding salt according to the composition, adding aqueous alkali into the solution to obtain white precipitate, drying, extruding, molding and roasting to obtain titanium-based composite oxide serving as a carrier;
(2) And (3) soaking the carrier in a heteropoly acid solution, and then drying and roasting to obtain the catalyst.
In the method, in the preparation process of the catalyst, the coprecipitation reaction time in the step (1) is 3-24 h. The drying temperature is 100-180 ℃, and the drying time is 8-24 h. The roasting temperature is 400-600 ℃, and the roasting time is 8-24 h. In the step (2), the dipping time is 6-24 h, the drying temperature is 100-160 ℃, the drying time is 6-12 h, the roasting temperature is 350-650 ℃, and the roasting time is 8-24 h.
In the method, the specific reaction conditions for the isobutene oligomerization are as follows: isobutene is used as a reaction raw material, and the reaction is carried out by the reaction of isobutene,taking heteropoly acid/titanium-based composite oxide as a catalyst, and the liquid hourly volume space velocity of isobutene is 0.5h -1 ～5.0h -1 Preferably 1.0h -1 ～4.0h -1 More preferably 1.5h -1 ～2.0h -1 (ii) a The reaction temperature is 80-150 ℃, preferably 90-130 ℃, and more preferably 100-120 ℃; the reaction pressure is 2.0 to 5.0MPa, preferably 2.0 to 4.5MPa, and more preferably 3.0 to 4.0MPa.
In the above process, the feedstock is a mixed C4 feedstock containing isobutene or pure isobutene. Wherein the mixed C4 feedstock has an isobutylene content of at least 5%, further at least 10%, and further at least 15% by weight.
The invention adopts heteropoly acid/titanium-based composite oxide as a catalyst for oligomerization of isobutene, and the catalyst shows higher dimer selectivity at relatively lower temperature. The catalyst has proper specific surface, pore size structure and acidity distribution, so that the acidity and activity of the catalyst are effectively regulated, and the defects of catalyst deactivation and conversion rate reduction caused by easy thermal decomposition, easy loss of acid amount and difficult separation of the Keggin structure of heteropoly acid in the heteropoly acid catalyst loaded by the single-component porous medium carrier are overcome. The method can realize continuous production, has simple and convenient operation in the reaction process, has the advantages of high conversion rate, good dimer selectivity and the like when being used for the isobutene oligomerization reaction, and is a new green and environment-friendly process.
Detailed Description
The invention is described in detail below with reference to specific examples, which are provided to understand and explain the invention, but not to limit the invention.
Example 1
(1) Preparing an aqueous solution a with the mass concentration of 25% by using 20g of aluminum nitrate and 25g of titanium tetrachloride, preparing an alkaline solution b of potassium hydroxide with the mass concentration of 20%, dropwise adding the solution b into the solution a at normal temperature under the stirring state, reacting for 10 hours to obtain a white pasty precipitate, washing, filtering, drying for 10 hours at 120 ℃, extruding and molding by using a conventional method, and roasting for 8 hours at 500 ℃ to obtain the titanium-based composite oxide carrier.
(2) 15g of phosphomolybdic acid is dissolved in 200mL of deionized water, the formed and roasted catalyst carrier is soaked in heteropoly acid solution for 8 hours, the soaked substance is dried for 10 hours at 120 ℃, and the catalyst is roasted for 10 hours at 450 ℃ to prepare the catalyst, and the composition of the catalyst is shown in Table 1.
(3) The prepared catalyst is used for the oligomerization of isobutene, the reaction is carried out in a stainless steel fixed bed reactor with phi 18mm multiplied by 1200mm, 30mL of the catalyst is filled in the reactor, quartz sand with the diameter of phi 0.5 mm-1.2 mm is respectively filled in the top and the bottom of the reactor, after the reactor is installed, nitrogen is used for replacing three times, the airtight test is qualified, isobutene and ethanol are sent into a preheater by a metering pump, and the volumetric space velocity of isobutene feeding is 1.5h -1 The reaction temperature was 90 ℃ and the reaction pressure was 3.0MPa, the test results are shown in Table 2.
Examples 2 to 5
The other conditions were the same as in example 1 except that the amounts of aluminum nitrate and phosphomolybdic acid were changed to obtain catalysts of different compositions, as shown in Table 1, and the reaction temperature was adjusted for the oligomerization of isobutylene, as shown in Table 1, and the results of the conversion of isobutylene and the dimer selectivity are shown in Table 2.
Example 6
The other conditions were the same as in example 1 except that aluminum nitrate was changed to zirconium tetrachloride and phosphomolybdic acid was changed to silicomolybdic acid to obtain catalysts having different compositions and compositions, as shown in Table 1, and the results for oligomerization of isobutylene as shown in Table 2.
Examples 7 to 10
The other conditions were the same as in example 6 except that the amounts of zirconium tetrachloride and silicomolybdic acid were varied to obtain catalysts of different compositions, as shown in Table 1, and the results for the oligomerization of isobutylene as shown in Table 2.
Example 11
The other conditions were the same as in example 1 except that aluminum nitrate was changed to silicon tetrachloride and phosphomolybdic acid was changed to phosphotungstic acid to obtain catalysts of different compositions and compositions, as shown in Table 1, and the results for the oligomerization of isobutylene as shown in Table 2.
Examples 12 to 15
The other conditions were the same as in example 11 except that the amounts of silicon tetrachloride and phosphotungstic acid were changed to obtain catalysts of different compositions, as shown in Table 1, and the results for the oligomerization of isobutylene as shown in Table 2.
Example 16
The other conditions were the same as in example 1 except that the amount of aluminum nitrate was changed, the amount of phosphomolybdic acid was changed to silicotungstic acid and the amount was changed to obtain catalysts of different compositions and compositions, as shown in Table 1, and the reaction results are shown in Table 2.
Example 17
The other conditions were the same as in example 1 except that the amount of aluminum nitrate was changed, the amount of phosphomolybdic acid was changed to arsenic tungstic acid and the amount was changed to obtain catalysts of different compositions and compositions, as shown in Table 1, and the reaction results were as shown in Table 2.
Example 18
The other conditions were the same as in example 1 except that the amount of aluminum nitrate was changed, the amount of phosphomolybdic acid was changed to germanotungstic acid and the amount was changed to obtain catalysts of different compositions and compositions, as shown in Table 1, and the reaction results are shown in Table 2.
Example 19
The other conditions were the same as in example 1 except that the amount of aluminum nitrate was changed, the amount of phosphomolybdic acid was changed to arsenomolybdic acid and the amounts thereof were changed to obtain catalysts of different compositions and compositions, as shown in Table 1, and the reaction results were as shown in Table 2.
Comparative example 1
Impregnation of TiO with aqueous phosphomolybdic acid solution 2 The carrier is dried for 12h at 110 ℃ and then roasted for 12h at 500 ℃ to prepare the catalyst. The catalyst was used in the oligomerization of isobutene under the same operating conditions as in example 1, the catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.
Comparative example 2
The other conditions were the same as in comparative example 1 except that phosphomolybdic acid was changed to phosphotungstic acid, the catalyst composition was as shown in Table 1, and the reaction results were as shown in Table 2.
Comparative example 3
The other conditions were the same as in comparative example 1 except that phosphomolybdic acid was changed to phosphotungstic acid, the catalyst composition was as shown in Table 1, and the reaction results were as shown in Table 2.
TABLE 1
Figure 974784DEST_PATH_IMAGE001
TABLE 2
Figure 816839DEST_PATH_IMAGE002
/>

Claims (5)

1. The method for oligomerization of isobutene is characterized by using heteropolyacid/titanium-based composite oxide as catalyst, in which the titanium-based composite oxide is selected from TiO 2 -Al 2 O 3 、TiO 2 -SiO 2 And TiO 2 -ZrO 2 At least one of heteropolyacids selected from at least one of phosphotungstic acid, silicotungstic acid, arsotungstic acid, germanotungstic acid, phosphomolybdic acid, silicomolybdic acid, arsenomolybdic acid and germanomolybdic acid; the weight ratio of the heteropoly acid to the titanium-based composite oxide in the catalyst is 0.05-1:1; tiO in the titanium-based composite oxide 2 The weight content of (A) is 10-90%;
the heteropoly acid/titanium-based composite oxide catalyst is prepared by the following method:
(1) Preparing a titanium-based composite oxide by adopting a coprecipitation method: preparing solution by taking corresponding salt according to the composition, adding aqueous alkali into the solution to obtain white precipitate, drying, extruding, forming and roasting to obtain titanium-based composite oxide as a carrier;
(2) Soaking the carrier in a heteropoly acid solution, drying and roasting at the roasting temperature of 350-450 ℃ to obtain the catalyst;
the specific reaction conditions for the isobutene oligomerization are as follows: isobutene is used as a reaction raw material, heteropoly acid/titanium-based composite oxide is used as a catalyst, and the liquid hourly volume space velocity of the isobutene is 0.5h -1 ～5.0h -1 The reaction temperature is 80-150 ℃, and the reaction pressure is 2.0-5.0 MPa.
2. The method according to claim 1, wherein the weight ratio of the heteropolyacid to the titanium-based composite oxide in the catalyst is from 0.1 to 0.9.
3. The method according to claim 1, wherein the weight ratio of the heteropolyacid to the titanium-based composite oxide in the catalyst is from 0.3 to 0.7.
4. The method of claim 1, wherein the titanium-based composite oxide is TiO 2 The weight content of (A) is 15-85%.
5. The process of claim 1 wherein the feedstock is a mixed C4 feedstock containing isobutylene or pure isobutylene, wherein the mixed C4 feedstock has an isobutylene content of at least 5% by weight.
CN201811622912.7A 2018-12-28 2018-12-28 Method for oligomerization of isobutene Active CN111377786B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811622912.7A CN111377786B (en) 2018-12-28 2018-12-28 Method for oligomerization of isobutene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811622912.7A CN111377786B (en) 2018-12-28 2018-12-28 Method for oligomerization of isobutene

Publications (2)

Publication Number Publication Date
CN111377786A CN111377786A (en) 2020-07-07
CN111377786B true CN111377786B (en) 2023-04-07

Family

ID=71220795

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811622912.7A Active CN111377786B (en) 2018-12-28 2018-12-28 Method for oligomerization of isobutene

Country Status (1)

Country Link
CN (1) CN111377786B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005015383A (en) * 2003-06-26 2005-01-20 Idemitsu Kosan Co Ltd Method for producing olefin oligomer
CN102909081A (en) * 2011-08-01 2013-02-06 中国石油化工股份有限公司 Catalyst and method for preparing methyl sec-butyl ether

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE578158A (en) * 1958-04-28
KR20120136363A (en) * 2010-03-17 2012-12-18 다이치 키겐소 카가쿠 코교 컴퍼니 리미티드 Catalyst for olefin oligomerization reaction
CN103044213B (en) * 2011-10-17 2016-01-20 中国石油化工股份有限公司 A kind of processing method preparing Ethyl Tertisry Butyl Ether

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005015383A (en) * 2003-06-26 2005-01-20 Idemitsu Kosan Co Ltd Method for producing olefin oligomer
CN102909081A (en) * 2011-08-01 2013-02-06 中国石油化工股份有限公司 Catalyst and method for preparing methyl sec-butyl ether

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
含氟固体酸催化剂上的异丁烯齐聚反应;龚洁;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20150715;B014-403 *
龚洁.含氟固体酸催化剂上的异丁烯齐聚反应.《中国优秀硕士学位论文全文数据库 工程科技I辑》.2015, *

Also Published As

Publication number Publication date
CN111377786A (en) 2020-07-07

Similar Documents

Publication Publication Date Title
JP4364126B2 (en) Method for producing dimethyl ether from methanol
CN101332432B (en) Load-type solid acid catalyst with selective oligomerisation for mixed C4
CN101190860A (en) Dimerization-etherification method for producing MTBE, isooctene and diisobutylene from C4 olefin
CN107737605B (en) Catalyst for selectively synthesizing 4-methyl-2, 6-di-tert-butylphenol and application thereof
CN107694599B (en) Catalyst for synthesizing 4-methyl-2, 6-di-tert-butylphenol and application thereof
CN101584991B (en) Catalyst for olefin catalytic cracking to produce propylene and ethylene and application thereof
CN111377786B (en) Method for oligomerization of isobutene
CN103044213B (en) A kind of processing method preparing Ethyl Tertisry Butyl Ether
CN101590421A (en) The catalyst of a kind of olefin catalytic cracking to produce propylene and ethene and application thereof
CN111377787B (en) Oligomerization reaction method of isobutene
CN111375433B (en) Method for oligomerization of isobutene
CN113024336B (en) Method for preparing isodecene by catalyzing isoamylene dimerization
CN101402540B (en) Method for producing isooctene with coproduction of sec-butyl carboxylate with selective superposition of butylene
CN111995491B (en) Preparation method of C12 olefin
CN103418379B (en) Remove the Catalysts and its preparation method of alkadienes in carbon four
CN112452330B (en) Process for producing propylene oligomer and propylene oligomer prepared by same
US11674091B2 (en) Catalytic cracking gasoline prehydrogenation method
CN111377788B (en) Method for oligomerization of isobutene
CN107185560A (en) A kind of olefin oligomerization catalyst and preparation method
CN103044214B (en) Preparation method of ethyl tert butyl ether
CN103044212B (en) Process method for preparing ethyl tert-butyl ether
CN1810373A (en) Catalyst for selective dimerization of isobutene
CN113582799B (en) Method for preparing isooctene by mixed carbon four-selectivity superposition with low 1-butene loss
CN1307132C (en) Catalyst for producing diesel oil from tetracarbon olefin polymerization and its preparation method and uses
CN114762832B (en) Preparation method and application of catalyst for producing mixed propylbenzene by alkylation of benzene and carbon tetraolefin

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20231120

Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee after: CHINA PETROLEUM & CHEMICAL Corp.

Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd.

Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee before: CHINA PETROLEUM & CHEMICAL Corp.

Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp.

TR01 Transfer of patent right